US3677693A - Method of milling and resin treating keratinous fibers - Google Patents

Method of milling and resin treating keratinous fibers Download PDF

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Publication number
US3677693A
US3677693A US90106A US3677693DA US3677693A US 3677693 A US3677693 A US 3677693A US 90106 A US90106 A US 90106A US 3677693D A US3677693D A US 3677693DA US 3677693 A US3677693 A US 3677693A
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resin
fabric
milling
resins
liquor
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US90106A
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English (en)
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Brian Robinson
Stephen Harvey Fillingham
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BASF Schweiz AG
IWS Nominee Co Ltd
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Ciba AG
IWS Nominee Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M13/522—Fulling
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process

Definitions

  • the invention relates to the finishing of textile fabrics consisting wholly or partially of keratinous fibres such as wool.
  • the fabric is milled and simultaneously treated with a resin imparting shrink-resistance to it by agitating it in an organic liquid containing the dissolved resin and emulsified water, separating excess liquor from the fabric and curing the resin remaining on the fabric.
  • the resins are preferably such as will cross-link in the reactive centres on the fibres, with a co-reactant or with itself, and especially polythiol resins containing at least two thiol groups per molecule, and cross-linking catalysts may be added to the milling liquor.
  • the process is particularly useful for knitted fabrics and garments, although it is also applicable to woven fabrics.
  • the present invention relates to a method of milling textile fabrics, including garments, containing keratinous fibres, and simultaneously treating them with a resin imparting shrink-resistance. It is particularly useful for knitted goods but is also of value for woven goods which require a milled finish.
  • the process of milling and making shrink-resistant fabrics is normally'a two-stage process.
  • the milling stage which enhances the appearance and handle of the goods, may be carried out by a number of methods, a recent example of which is the so-called solvent-milling method in which the goods are agitated, e.g. by tumbling, in an emulsion of water and an organic solvent.
  • imparting shrink-resistance may be carried out by a number of diiferent methods, the more important of which are the resin treatment methods, and the application of resin to the fabric has to follow the milling stage because milling can not effectively be carried out on a fabric already treated to make it shrink-resistant.
  • a process for milling a textile fabric, consisting wholly or partially of keratinous fibres and simultaneously treating it with a resin imparting shrink-resistance thereto comprises organic solvent containing (i) a resin which imparts shrink-resistance dissolved therein ii) water emulsified therein,
  • the degree of milling depends on the extent of the agitation applied to the fabric and the amount of water present. Generally, water concentrations in the range of 2 to 30% of the dry weight of the fabrics (a ratio of 1:50 to 1:3) are required.
  • dry weight is meant the Weight of wool in equilibrium with the moisture of its atmosphere
  • a surface active agent which will facilitate the milling process and which will also assist in the production and stabilisation of the emulsion formed by the water and organic solvent.
  • Cationic, nonionic, and anionic surface active agents may be used but it is found that there is less interference in obtaining a shrink-resist finish when cationic surface active agents are used. The latter type also have the advantage of reducing electrostatic problems and of leaving the goods with a soft handle.
  • surface active agents which are suitable for the present process are known as milling aids or dry-cleaning soaps.
  • the amount of surface active agent present in the emulsion may vary between wide limits but generally satisfactory results are obtained if the amount used lies in the range 1 to 30 grams per litre of emulsion, preferably in the range 2 to 20 grams per litre.
  • the amount of surface active agent is preferably from 1 gram per 10 ml. water to 10 gram per ml. water, and usually about 1 gram per 3 ml. water.
  • the degree of milling action depends to a large extent on the agitational forces applied to the fabric and these forces may be applied by any convenient piece of textile machinery which has a container provided with means for agitating a fabric therein.
  • the conventional dry-cleaning machine Where the fabric is tumbled in a rotating drum and, in the process according to the invention, the emulsion may be formed in the drum either before or after the fabric is inserted and subjected to the tumbling action.
  • the ratio (w./v.) of fabric to solvent is conveniently from 1:70 to 1:6, but most usually about 1: 10 (i.e. grams:1 litre).
  • the organic solvent employed may be any of those which are harmless to keratinous fibres, e.g. white spirit, and is preferably one which is used in the dry-cleaning industry: these are usually liquid halogenated hydrocar bons, particularly chlorinated and chlorinated/fluorinated low molecular weight solvents containing 1 to 4 carbon atoms, e.g. perchloroethylene, trichloroethylene, carbon tetrachloride, 1,1,2 trichloro 1,2,2-trifluoroethane and 1,1,1-trichloroethane.
  • the solvent-soluble resin may be any resin which imparts to the fabric a shrink-resistant finish and which has no reaction with water.
  • resins which are used to impart shrink-resistant properties and which contain functional groups capable of reacting with water under the conditions used, e.g. those containing acid chlorides; resins of this type cannot be used in the process,
  • Polyisocyanates can be used if they are blocked or if they react sufficiently slowly with water. It is preferable that, as well as being soluble in the organic solvent, the resins should be insoluble in water. It is believed that the resin should be capable of being cross-linked with itself, with reactive centres on the keratinous fibres, or with them both. The resin may also be cross-linked with another substance (a coreactant) on the keratinous fibres.
  • suitable resins are the solvent-soluble acrylics, polybutadienes, carboxylated polybutadienes, silicones, polyepoxides and polythiols.
  • the acrylic resins are polymers and co-polymers of acrylic acid, acrylamide, acrylonitrile and alkyl and hydroxyalkyl esters of acrylic acid with C to C aliphatic alcohols; also the methacrylic analogues of these. Those which are more suitable are those which are soft, i.e. have a glass transition temperature of below 0 C. and are cross-linkable.
  • the preferred polybutadienes are those having a molecular weight in the range 2,500 to 50,000 and may contain methyl or chloromethyl substituents.
  • the carboxylated polybutadienes which may be used in the invention can be prepared by reacting such polybutadienes with mercaptocarboxylic acids.
  • the preferred silicones are polydimethyl siloxanes having an average molecular weight of at least 1,000.
  • Polyepoxides which may be used include polyglycidyl ethers of polyhydric phenols having an epoxide content of at least 1 equiv./kg.
  • the preferred polythiols are those having, per molecule, two or more SH groups directly attached to aliphatic carbon atoms. Those which have been found to be particularly useful are those having a polyoxyalkylene backbone to which are attached the thiol, i.e. mercaptan, groups. Alternatively, the backbone may be a polyester structure or a structure containing alkyleneoxy and polysulphide units. Excellent results have been obtained with the class of polythiol resins having at least two thiol groups per molecule and containing:
  • the most important resins of this class may be defined as those prepared by the reaction of a polyhydric alcohol with an alkylene oxide followed by esterification of the terminal hydroxy groups with a mercaptocarboxylic acid, preferably thioglycollic acid.
  • a mercaptocarboxylic acid preferably thioglycollic acid.
  • An example of such a resin is Thiol Resin A as described in Example 1.
  • the preferred amount of the resin applied to the fabric lies in the range 0.5 to 15% by weight (1:200 to 1:7 ratio), preferably in the range 1 to 5% by weight, of dry fabric.
  • the milling liquor containing the requisite amount of water emulsified therein is a cloudy solution, and when the fabric is agitated in this solution it gradually clarifies as the water passes from the emulsion on to the goods. Such a change in the appearance of the solution is a convenient indication of when the point of complete water retention by the fabric is reached, and at this point the desired amount of milling in the presence of the liquor has, in most cases, been carried out.
  • the agitation period is usually from 1 to 25 minutes.
  • excess liquor is drained from the fabric, preferably to leave to 500% by weight of liquor thereon. Draining may be effected by simply allowing excess liquor to run from the container holding the milling liquor but when a dry-cleaning machine is used excess liquor may be centrifuged from the fabric by using the hydro-extract cycle. When draining is completed it is preferable to maintain the wet fabric in a state of agitation for a further period to complete substantially the milling of the fabric; such a further period may last from about 1 to 10 minutes. This period of agitating the wet fabric is normally required for the majority of fabrics.
  • the fabric may then be stored to allow the resin constituent of the liquor to cure and thus obtain the maximum shrink-resistant effect.
  • the precise curing conditions selected for any particular resin must depend on its chemical and physical properties but generally speaking mild heating will be advantageous for all resins, for example heating to a temperature in the range 25 to 120 or up to 150 C.
  • the curing of the resin may also be accelerated by using an appropriate catalyst and/ or coreactant which may be incorporated in the solvent or the Water of the milling liquor or may be applied to the fabric before or after treatment commences.
  • the acrylic resins may be cross-linked by reaction with aminoplasts, epoxide resin or phenoplasts; the reaction may be accelerated by selection of an appropriate catalyst.
  • strong acids such as toluene-p-sulphonic acid may be used to catalyse the reaction of hydroxyl-containing acrylic resins with aminoplasts.
  • Some types of acrylic resin e.g. those based on N-(hydroxymethyl)acrylamide are self-linkable and the curing reaction can be accelerated by strong acids.
  • Catalysts for the curing of polybutadienes and carboxylated polybutadienes include siccatives such as cobalt octoate, iron naphthenate or manganese naphthenate.
  • the cure of the silicones may be accelerated by using siccatives such as those listed above, organometallic compounds, e.g. dibutyltin dilaurate or free radical catalysts such as peroxides or hydroperoxides, e.g. dibenzoyl peroxides.
  • organometallic compounds e.g. dibutyltin dilaurate
  • free radical catalysts such as peroxides or hydroperoxides, e.g. dibenzoyl peroxides.
  • Epoxide resins may be cross-linked by reaction with co-reactants such as polyamines and poly(aminoamides) or by homopolymerisation by using tertiary amines, or Lewis acids such as as BCl
  • co-reactants such as polyamines and poly(aminoamides) or by homopolymerisation by using tertiary amines, or Lewis acids such as as BCl
  • Lewis acids such as as BCl
  • BCl Lewis acids
  • organic and inorganic bases siccatives, free-radical catalysts, and oxidative curing agents.
  • organic bases there may be used primary or secondary amines such as the lower alkanolamines, e.g. monoand di-ethanolamine (MBA and DEA), and polyamines, e.g.
  • ethylendiamine diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, hexamethylenediamine (HMD), and polyethyleneimine (PEI).
  • inorganic bases there may be used the water-soluble oxides and hydroxides, e.g. sodium hydroxide, or ammonia, sodium carbonate, bicarbonate or sodium tetraborate. All these catalysts are water-soluble and can be included in the milling water. Solvent-soluble catalysts can also be used and are applied with the resin in the solvent.
  • Examples include siccatives such as calcium, copper, iron, lead, cerium, and cobalt naphthenates, and free-radical catalysts, for example peroxides and hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate and bis(4-chlorobenzoyl) peroxide.
  • peroxides and hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate and bis(4-chlorobenzoyl) peroxide.
  • catalysts include sulphur, and sulphur-containing organic compounds in which the sulphur is not exclusively present in mercaptan groups, namely, mercaptobenzothiazoles or derivatives thereof, dithiocarbamates, thiuram sulphides, thioureas, dialkyl, dicycloalkyl, or diaralkyl disulphides, alkyl xanthogen disulphides, and alkyl xanthates.
  • Yet other catalysts are salts of a heavy metal with an acid having an acid strength (log pK) below 5, or chelates of a heavy metal, ineluding chelates which are also salts.
  • heavy metal is meant one classified as heavy in Langes Handbook of Chemistry, revised 10th edition, McGraw-Hill Book Co., at pp. 60-61, that is, a metal of Group I-B, II-B, III-B, IV-B, V-B, VI-B, VII-B, or VIII, a metal of Group III-A having an atomic number of at least 13, a metal of Group IV-A having an atomic number of at least 32, or a metal of Group V-A having an atomic number of at least 51.
  • the metal is a member of Group I-B, II-B, IV-B, V-B, VI-B, VII-B, or VIII, particularly the first series of such metals, i.e.
  • Suitable salt-forming, non-drying acids are mineral acids, especially hydrochloric, hydrobromic, nitric, sulphuric, phosphorous, and phosphoric acids, and organic acids such as chloroacetic, fumaric, maleic, oxalic, salicyclic, and more especially citric acid.
  • Suitable chelating agents include those in which the chelating atoms are oxygen and/or nitrogen, for example, 1,2- and 1,3-diketones such as acetylacetone, alkylenediamines such as ethylenediamine, and more particularly ethylenediaminetetracetic acid.
  • the amount of catalyst employed preferably lies in the range 0.001 to 10% based on the weight of the fabric.
  • fabric as used throughout this specification covers garments, garment pieces, piece goods or other fabric items which require a milling and shrinkresistant treatment. Generally speaking knitted goods will be in garment form and woven goods in the piece.
  • tion refers to fibres which ma ybe derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair, and llama but preferably are fibres derived from sheeps wool.
  • the keratinous fibres may also be blended with other fibrous or filamentary material, e.g. polyamides, polyesters, polyacrylonitriles, silk, cotton, and regenerated cellulose. It has been found that the process is particularly applicable to .the milling and shrink-resistant treatment of Shetland and lambswool knitted garments.
  • the fabric .. is preferably subjected to a conventional scouring step to remove contaminants, e.g. oil, from the fabric.
  • a conventional scouring step to remove contaminants, e.g. oil, from the fabric.
  • the scouring may be performed as a pretreatment in the same machine and in these circumstances it is unnecessary to dry the scoured fabric before .carryingout the process of mill: ing and imparting shrink-resistance.
  • Thiol Resins B-G' These polymercaptans were prepared as described for Thiol Resin Aexcept that in the case of resins E-G perchloroethylene 'was used instead of toluene and for resins E4) the reaction mixture was not washed with Thiol Resin H
  • Thiokol -LP-3 which, according to the manufacturers, Thiokol Chemical Corporation, had an average molecular weight of 1,000, a viscosity at 27 C. of 700-1200 centipoises and 2% cross-linking.
  • the structure is substantially that represented by the formula (C2H404SS 6C2H4OCHzOC2H4SH Thiol Re sin I A mixture of 23 g.
  • Epoxide Resin I This denotes a polyglycidyl ether of 2,2'-bis(p-hydroxyphenyl)propane having an epoxide content of 5.2 equiv./kg.
  • Poly(aminoamide) Resin I Denotes'a poly(aniinoamide) made from diethylenetriamine and a mixture of dimerised and trimerised unsaturated monocarboxylic acids, having an amine value equivalent of 350400 mg. KOH/g.
  • Poly(aminoamide) Resin II Denotes a similar product having an amine value equivalent of 210-230 mg. KOH/g.
  • Melamine Resin I is a n butylated melamine-formaldehyde resin of 63- 67% solids content in n-butanol supplied by HP Chemicals (U.K.) Ltd., London, under the designation Epok U 9193.
  • Acrylic Resin I Denotes a cross-linkable acrylic resin containing hydroxyl groups supplied at 54-56% solids content under 1 the designation 'Epok D 2100 by BP Chemicals (U.K.)
  • Acrylic Resin -II Is a solvent-polymerised viscous'acrylic ester polymer of 40% active content in methanol-ethyl acetate.
  • Catalyst MS Contains 10% active substance in methanol-ethyl acetate.
  • Lambswool and Shetland knitted samples 500 g.) were solvent-scoured in perchloroethylene in a dry-cleaning machine, and were centrifugally extracted. The goods i were tumbled in an emulsion of water and catalyst in gg g lambswool sweater 1/13 cover a solution of resin and milling aid in perchloroethylene until all the water and catalyst had been exhausted on Examp 1e Kmtted Shetland Sweater 2/10 F
  • Example 6 Woollen woven piece; 420 g./sq. m.
  • Example 7 50:50 vicose/wool blend; 422 g./sq. m.
  • the formulation of the milling bath was as WASH TEST RESULTS follows: Percent resin Perchloroethylene-S litres applied Percent area felting Milling Agent KFS (Allied Colloids)75 g. gg gg gg Shrmkage Thiol Resin A-320 g. mp fabric) Mild wash Full wash Catalyst (see below)4% on weight of wool Water-25% on weight of wool a 22 The liquor was then allowed to drain back to the milllg ing tank and the samples extracted to leave a proportion 24 61 0f the solution on the goods. After being tumbled to Cont-m1 3-8 8 bring up the milled finish, the goods were dried off to leave the resin on the surface of the fibres. EXAMPLES 1047 The following time cycle was used:
  • Such catalysts include siccatives and organic peroxides. These examples are conducted as Examples 6-9 but the water is milled onto the goods and the catalyst applied with the resin from the solvent phase. 3% resin (on the weight of wool) was used.
  • a process for milling a textile fabric consisting at least partially of keratinous fibres and simultaneously treating it with a resin imparting shrink-resistance comprising the steps of (a) agitating the fabric in a milling liquor which is an organic liquid containing (i) a resin which imparts shrink-resistance dissolved therein; (ii) water emulsified therein;
  • said resin is selected from the group consisting of polythiol, polyepoxide, acrylic, polybutadiene, carboxylated polybutadiene and silicone resins.
  • a process according to claim 1 in which a catalyst is dissolved in the organic phase of said milling liquor in an 25 amount corresponding to 0.001 to 10% by weight of the fabric.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatment Of Fiber Materials (AREA)
US90106A 1969-11-18 1970-11-16 Method of milling and resin treating keratinous fibers Expired - Lifetime US3677693A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119089A1 (en) * 2001-09-25 2003-06-26 Dyke Mark Van Methods for controlling peptide solubility, chemically modified peptides, and stable solvent systems for producing same
US20030204037A1 (en) * 2002-04-10 2003-10-30 Van Dyke Mark E. Methods for producing, films comprising, and methods for using heterogeneous crosslinked protein networks
US20030219486A1 (en) * 2002-04-10 2003-11-27 Van Dyke Mark E. Methods for producing, films comprising, and methods for using heterogenous crosslinked protein networks
US20030224052A1 (en) * 2002-04-22 2003-12-04 Van Dyke Mark E. Hydrogel with controllable merchanical, chemical, and biological properties and method for making same
US20040062793A1 (en) * 2002-07-05 2004-04-01 Dyke Mark Van Tissue defect dressings comprising proteinaceous networks
US20040120910A1 (en) * 2002-04-10 2004-06-24 Dyke Mark Van Methods for producing, films comprising, and methods for using heterogeneous crosslinked protein networks
WO2003087195A3 (en) * 2002-04-10 2004-07-15 Keraplast Tech Ltd Heterogeneous protein networks crosslinked with silicone-containing links, and methods for producing them
US20050058686A1 (en) * 2002-07-25 2005-03-17 Mark Van Dyke Bioactive coating for medical devices

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119089A1 (en) * 2001-09-25 2003-06-26 Dyke Mark Van Methods for controlling peptide solubility, chemically modified peptides, and stable solvent systems for producing same
US7001988B2 (en) 2001-09-25 2006-02-21 Keraplast Technologies, Ltd. Methods for controlling peptide solubility, chemically modified peptides, and stable solvent systems for producing same
US6989437B2 (en) 2002-04-10 2006-01-24 Keraplast Technologies, Ltd. Methods for producing, films comprising, and methods for using heterogeneous crosslinked protein networks
US20040120910A1 (en) * 2002-04-10 2004-06-24 Dyke Mark Van Methods for producing, films comprising, and methods for using heterogeneous crosslinked protein networks
WO2003087195A3 (en) * 2002-04-10 2004-07-15 Keraplast Tech Ltd Heterogeneous protein networks crosslinked with silicone-containing links, and methods for producing them
US6914126B2 (en) 2002-04-10 2005-07-05 Keraplast Technologies, Ltd. Methods for producing, films comprising, and methods for using heterogenous crosslinked protein networks
US20030219486A1 (en) * 2002-04-10 2003-11-27 Van Dyke Mark E. Methods for producing, films comprising, and methods for using heterogenous crosslinked protein networks
US20030204037A1 (en) * 2002-04-10 2003-10-30 Van Dyke Mark E. Methods for producing, films comprising, and methods for using heterogeneous crosslinked protein networks
US20030224052A1 (en) * 2002-04-22 2003-12-04 Van Dyke Mark E. Hydrogel with controllable merchanical, chemical, and biological properties and method for making same
US7001987B2 (en) 2002-04-22 2006-02-21 Keraplast Technologies, Ltd. Hydrogel with controllable mechanical, chemical, and biological properties and method for making same
US20040062793A1 (en) * 2002-07-05 2004-04-01 Dyke Mark Van Tissue defect dressings comprising proteinaceous networks
US20050058686A1 (en) * 2002-07-25 2005-03-17 Mark Van Dyke Bioactive coating for medical devices
US20090148488A1 (en) * 2002-07-25 2009-06-11 Keraplast Technologies, Ltd. Bioactive coating for medical devices

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ES385864A1 (es) 1973-05-01
CH1706870A4 (enrdf_load_html_response) 1974-04-30
DE2056083A1 (de) 1971-05-27
HU162457B (enrdf_load_html_response) 1973-02-28
CH555927A (enrdf_load_html_response) 1974-11-15
PL81700B1 (enrdf_load_html_response) 1975-08-30
IL35647A (en) 1974-09-10
AT313847B (de) 1974-03-11
BE758986A (fr) 1971-04-30
FR2067367B1 (enrdf_load_html_response) 1974-08-23
CA941558A (en) 1974-02-12
FR2067367A1 (enrdf_load_html_response) 1971-08-20
GB1327395A (en) 1973-08-22
IE34717L (en) 1971-05-18
IL35647A0 (en) 1971-01-28
NL7016661A (enrdf_load_html_response) 1971-05-21
JPS4921280B1 (enrdf_load_html_response) 1974-05-30
ZA707691B (en) 1971-08-25

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